The influence of molecular weight (Mw) on the structural evolution of as cast amorphous poly (ethylene naphthalene), PEN, during uniaxial stretching and further relaxation is investigated by real time measurement of the true mechanical and optical behavior of the material in the rubbery state. Uniaxial deformation behavior reveals that stress-optical behavior is composed of three regions: (I) traditional stress optical region where the polymer remains amorphous, (II) fast birefringence increase region that accompany rapid rise in crystallinity and (III) birefringence saturation region. Both materials follow the stress optical rule (SOR) at low deformation levels with a stress optical constant of 27.5 GPa-1. Stress-optical behavior deviates from linearity in both MW PEN's when crystallinity exceeds 7% and the material exhibit nematic order. The deviation from linearity occurs at lower stress levels for the low MW material, nevertheless. The mechanism of neck formation has a considerable influence on the crystallization of the material. After neck starts the crystallinity increases rapidly in both materials, reaching a saturation value of approx. 35% in crystallinity when strain hardening occurs. The preliminary studies revealed that the relaxation behavior of PEN involves a complete orientation recovery following the stress optical rule when the material is first stretched within the Region I and if stretched beyond the linear range the relaxation stage is found to accompany partial orientation relaxation followed by crystallization.
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